JP5131245B2 - Method for analyzing metal impurities in silicon powder - Google Patents
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- JP5131245B2 JP5131245B2 JP2009123517A JP2009123517A JP5131245B2 JP 5131245 B2 JP5131245 B2 JP 5131245B2 JP 2009123517 A JP2009123517 A JP 2009123517A JP 2009123517 A JP2009123517 A JP 2009123517A JP 5131245 B2 JP5131245 B2 JP 5131245B2
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- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims description 93
- 229910052751 metal Inorganic materials 0.000 title claims description 89
- 239000002184 metal Substances 0.000 title claims description 89
- 239000012535 impurity Substances 0.000 title claims description 87
- 239000011863 silicon-based powder Substances 0.000 title claims description 78
- 238000000034 method Methods 0.000 title claims description 28
- 239000011259 mixed solution Substances 0.000 claims description 86
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 54
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 47
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 22
- 238000004458 analytical method Methods 0.000 claims description 20
- 238000010438 heat treatment Methods 0.000 claims description 16
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 15
- 229910017604 nitric acid Inorganic materials 0.000 claims description 15
- 229910052710 silicon Inorganic materials 0.000 claims description 15
- 239000010703 silicon Substances 0.000 claims description 15
- 238000001704 evaporation Methods 0.000 claims description 9
- ABTOQLMXBSRXSM-UHFFFAOYSA-N silicon tetrafluoride Chemical compound F[Si](F)(F)F ABTOQLMXBSRXSM-UHFFFAOYSA-N 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 230000008020 evaporation Effects 0.000 claims description 7
- QOSATHPSBFQAML-UHFFFAOYSA-N hydrogen peroxide;hydrate Chemical compound O.OO QOSATHPSBFQAML-UHFFFAOYSA-N 0.000 claims description 3
- 230000008018 melting Effects 0.000 claims description 3
- 238000002844 melting Methods 0.000 claims description 3
- 238000000151 deposition Methods 0.000 claims description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 20
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 17
- 238000001095 inductively coupled plasma mass spectrometry Methods 0.000 description 11
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 10
- 239000010931 gold Substances 0.000 description 10
- 229910052737 gold Inorganic materials 0.000 description 9
- 229910052697 platinum Inorganic materials 0.000 description 9
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 8
- 229910052782 aluminium Inorganic materials 0.000 description 7
- 239000001257 hydrogen Substances 0.000 description 7
- 229910052739 hydrogen Inorganic materials 0.000 description 7
- 229910052742 iron Inorganic materials 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 239000002245 particle Substances 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 5
- 239000004810 polytetrafluoroethylene Substances 0.000 description 5
- 239000004065 semiconductor Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- QZPSXPBJTPJTSZ-UHFFFAOYSA-N aqua regia Chemical compound Cl.O[N+]([O-])=O QZPSXPBJTPJTSZ-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- -1 iron and aluminum Chemical class 0.000 description 3
- 238000003754 machining Methods 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 229920001296 polysiloxane Polymers 0.000 description 3
- 239000010802 sludge Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 2
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- VPCDQGACGWYTMC-UHFFFAOYSA-N nitrosyl chloride Chemical compound ClN=O VPCDQGACGWYTMC-UHFFFAOYSA-N 0.000 description 2
- 235000019392 nitrosyl chloride Nutrition 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229910052814 silicon oxide Inorganic materials 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000006199 nebulizer Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 231100000167 toxic agent Toxicity 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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Description
本発明は、シリコン粉の金属不純物の分析方法、詳しくはシリコン粉の表面およびシリコン粉の内部に存在する金属の不純物の濃度を測定することが可能なシリコン粉の金属不純物の分析方法に関する。 The present invention relates to a method for analyzing metal impurities in silicon powder, and more particularly, to a method for analyzing metal impurities in silicon powder capable of measuring the concentration of metal impurities present on the surface of silicon powder and inside silicon powder.
太陽電池の原料において、現在シリコン粉が注目されている。このシリコン粉を固めて太陽電池結晶の原料として使用できるか否かの検討が行われている。この際、シリコン粉に含まれる金属不純物は、太陽電池の性能を著しく劣化させる一要因である。シリコン粉は、シリコンウェーハを加工する際、またデバイス形成後のウェーハのバックグラインド加工の際、シリコンスラッジなどに発生する。この場合、シリコンウェーハの加工機によって、シリコン粉に金属不純物が付着する。この金属不純物には、鉄、アルミニウムのようなイオン化傾向が水素より高い金属だけでなく、銅、白金、金などのイオン化傾向が水素より低い金属も含まれる。これら金属の不純物を充分な精度の下で分析し、管理していくことが非常に重要である。
シリコン粉に含まれる金属不純物の分析について現在まで報告されていないが、半導体屑に含まれる金属不純物を洗浄する方法として、特許文献１による方法がある。
特許文献１に係る金属不純物を洗浄する方法は、半導体を機械加工することにより発生する半導体屑に酸性を示す物質を混入して半導体屑の表面に付着した金属イオンを半導体屑から分離させる。この酸性を示す物質とは、塩酸、酢酸、クエン酸などである。
また、シリコン基板に含まれる微量不純物の濃度を分析する方法として、特許文献２による方法がある。
特許文献２では、微量不純物にフッ酸と硝酸の混酸溶液を加え、１５０℃〜２２０℃に加熱し、その後、この微量不純物にフッ酸と硝酸と硫酸の混酸溶液を加え、１５０〜２２０℃に加熱することにより、シリコン成分とボロン成分とを気化させ、気化させた後の残留物から不純物の濃度を分析する。
Silicon powder is currently attracting attention as a raw material for solar cells. It is being investigated whether or not this silicon powder can be hardened and used as a raw material for solar cell crystals. At this time, metal impurities contained in the silicon powder are one factor that significantly deteriorates the performance of the solar cell. Silicon powder is generated in silicon sludge and the like during processing of a silicon wafer and during back grinding of the wafer after device formation. In this case, metal impurities adhere to the silicon powder by the silicon wafer processing machine. The metal impurities include not only metals having a higher ionization tendency than hydrogen, such as iron and aluminum, but also metals having a lower ionization tendency, such as copper, platinum, and gold, than hydrogen. It is very important to analyze and manage these metal impurities with sufficient accuracy.
Although analysis of metal impurities contained in silicon powder has not been reported so far, there is a method according to Patent Document 1 as a method for cleaning metal impurities contained in semiconductor scrap.
The method for cleaning metal impurities according to Patent Document 1 separates metal ions adhering to the surface of the semiconductor scrap from the semiconductor scrap by mixing an acidic substance into the semiconductor scrap generated by machining the semiconductor. Examples of the substance exhibiting acidity include hydrochloric acid, acetic acid, citric acid and the like.
Further, as a method for analyzing the concentration of a trace impurity contained in a silicon substrate, there is a method according to Patent Document 2.
In Patent Document 2, a mixed acid solution of hydrofluoric acid and nitric acid is added to a small amount of impurities and heated to 150 ° C. to 220 ° C. Then, a mixed acid solution of hydrofluoric acid, nitric acid and sulfuric acid is added to the small amount of impurities, and the temperature is increased to 150 to 220 ° C. By heating, the silicon component and the boron component are vaporized, and the concentration of impurities is analyzed from the residue after the vaporization.
金属不純物の濃度は、ＩＣＰ発光分析、ＩＣＰ−ＭＳ、原子吸光分析等の分析機器により測定する。これらの分析方法は、金属不純物を溶液に溶解する必要がある。
しかしながら、特許文献１による金属不純物を洗浄する方法、および特許文献２による微量不純物の濃度を分析する方法によると、イオン化傾向が水素より低い銅、金や、白金等を溶解することができず、このため、ＩＣＰ発光分析などによる分析を行うことができなかった。また、シリコン粉の表面の金属不純物の分析しか行えず、シリコン粉の内部に存在する金属不純物の分析ができなかった。
そこで、この発明は、金や白金などのイオン化傾向が水素より低い物質でも溶液に溶解させ、ＩＣＰ−ＭＳ発光分析等の分析機器による分析が行えるシリコン粉の金属不純物の分析方法を提供することを目的とする。さらに、シリコン粉の表面に付着した金属不純物のみならず、シリコン粉の内部に存在する金属不純物を分析することが可能なシリコン粉の金属不純物の分析方法を提供することを目的とする。
The concentration of the metal impurity is measured by an analytical instrument such as ICP emission analysis, ICP-MS, atomic absorption analysis. These analytical methods require dissolution of metal impurities in the solution.
However, according to the method of cleaning metal impurities according to Patent Document 1 and the method of analyzing the concentration of trace impurities according to Patent Document 2, it is not possible to dissolve copper, gold, platinum or the like whose ionization tendency is lower than that of hydrogen, For this reason, analysis by ICP emission analysis or the like could not be performed. Further, only metal impurities on the surface of the silicon powder could be analyzed, and metal impurities existing inside the silicon powder could not be analyzed.
Therefore, the present invention provides a method for analyzing metal impurities in silicon powder, which can be dissolved in a solution even with a material having a lower ionization tendency than hydrogen, such as gold or platinum, and can be analyzed by an analytical instrument such as ICP-MS emission analysis. Objective. Furthermore, it aims at providing the analysis method of the metal impurity of the silicon powder which can analyze not only the metal impurity adhering to the surface of silicon powder but the metal impurity which exists in the inside of silicon powder.
請求項１に記載の発明は、金属不純物を含有したシリコン粉を第１の容器に投入し、塩酸および過酸化水素水、または、フッ酸および過酸化水素水からなる第１の混合溶液をこのシリコン粉に加え、所定時間静置することにより、上記シリコン粉の表面に付着している金属不純物を溶解する金属不純物溶解工程と、その後、上記シリコン粉を第１の容器から取り出し、第２の容器に入れ、塩酸と、硝酸と、フッ酸とからなる第２の混合溶液をこのシリコン粉に加え、四フッ化ケイ素を発生させ、この四フッ化ケイ素を第２の容器の外に放出するシリコン反応工程と、その後、この第２の混合溶液を蒸発させることにより金属不純物を析出させる蒸発工程と、上記蒸発工程後、析出した金属不純物に新たに第２の混合溶液を加え、これを加熱し、析出した金属不純物を溶解させる加熱溶解工程と、上記加熱溶解工程後、析出した金属不純物を溶解した第２の混合溶液を採取し、この第２の混合溶液に溶解した金属不純物の濃度を測定する金属分析工程と、を有するシリコン粉の金属不純物の分析方法である。 In the first aspect of the present invention, silicon powder containing metal impurities is put into a first container, and a first mixed solution composed of hydrochloric acid and hydrogen peroxide solution or hydrofluoric acid and hydrogen peroxide solution is added to the first container. In addition to the silicon powder, the metal powder is dissolved for a predetermined time to dissolve the metal impurities adhering to the surface of the silicon powder, and then the silicon powder is taken out from the first container, and the second Put in a container, add a second mixed solution of hydrochloric acid, nitric acid, and hydrofluoric acid to the silicon powder to generate silicon tetrafluoride, and release the silicon tetrafluoride to the outside of the second container. A silicon reaction step, and then an evaporation step for depositing metal impurities by evaporating the second mixed solution, and after the evaporation step, a second mixed solution is newly added to the deposited metal impurities and heated. Shi A heating and dissolving step for dissolving the precipitated metal impurities, and after the heating and dissolving step, a second mixed solution in which the precipitated metal impurities are dissolved is collected, and the concentration of the metal impurities dissolved in the second mixed solution is measured. A method for analyzing metal impurities in silicon powder.
請求項１に記載の発明によれば、第１の容器に金属不純物が付着したシリコン粉を入れる。そして、このシリコン粉に、第１の混合溶液（塩酸と過酸化水素水との混合溶液、またはフッ酸と過酸化水素水との混合溶液）を加え、所定時間静置する。このとき、シリコン粉の表面に付着した金属の不純物を溶解する。静置とは、容器に振動を与えずに、または容器内の内容物を撹拌せずに、第１の混合溶液とシリコン粉とを固液分離することである。
その後、シリコン酸化膜が表面に形成されたシリコン粉を第１の容器から取り出し、第２の容器、例えばＰＴＦＥ（Polytetrafluoroethylene）製の容器に入れ、このシリコン酸化膜が表面に形成されたシリコン粉に第２の混合溶液（塩酸と硝酸とフッ酸との混合溶液）を加え、四フッ化ケイ素を発生させ、この四フッ化ケイ素を第２の容器の外に放出する。その後、熱を加えて、第２の混合溶液を蒸発させる。この結果、金属不純物のみが析出する。
その後、析出した金属不純物に再度第２の混合溶液を加え、加熱する。この時、金属不純物は溶解し、金属不純物を回収することができる。
その後、第１の混合溶液と第２の混合溶液をそれぞれ分析する。
シリコン粉とは、シリコンインゴットを機械加工してウェーハを製造する工程や、デバイス形成後のウェーハのバックグラインド工程などで多量に発生するシリコンスラッジ等を指す。
金属不純物とは、鉄、アルミニウム、銅、チタン、金、白金等、イオン化傾向の高低に拘わらずすべての金属成分を指す。
According to the first aspect of the present invention, silicon powder with metal impurities attached is placed in the first container. Then, a first mixed solution (a mixed solution of hydrochloric acid and hydrogen peroxide solution or a mixed solution of hydrofluoric acid and hydrogen peroxide solution) is added to the silicon powder, and left for a predetermined time. At this time, metal impurities adhering to the surface of the silicon powder are dissolved. The standing is to solid-liquid separate the first mixed solution and the silicon powder without applying vibration to the container or stirring the contents in the container.
Thereafter, the silicon powder having the silicon oxide film formed on the surface is taken out from the first container and placed in a second container such as a PTFE (Polytetrafluoroethylene) container. A second mixed solution (mixed solution of hydrochloric acid, nitric acid, and hydrofluoric acid) is added to generate silicon tetrafluoride, and the silicon tetrafluoride is released out of the second container. Thereafter, heat is applied to evaporate the second mixed solution. As a result, only metal impurities are deposited.
Thereafter, the second mixed solution is added again to the deposited metal impurities and heated. At this time, the metal impurities are dissolved and the metal impurities can be recovered.
Thereafter, each of the first mixed solution and the second mixed solution is analyzed.
Silicon powder refers to silicon sludge and the like generated in a large amount in a process of manufacturing a wafer by machining a silicon ingot, a back grinding process of a wafer after device formation, and the like.
Metal impurities refer to all metal components, such as iron, aluminum, copper, titanium, gold, and platinum, regardless of the level of ionization.
請求項２に記載の発明は、上記第１の混合溶液は、１．０〜３７ｖｏｌ％の塩酸と、１．０〜２０ｖｏｌ％の過酸化水素水との混合溶液、または、１．０〜１０ｖｏｌ％のフッ酸と、１．０〜２０ｖｏｌ％の過酸化水素水との混合溶液である請求項１に記載のシリコン粉の金属不純物の分析方法である。 In the invention according to claim 2, the first mixed solution is a mixed solution of 1.0 to 37 vol% hydrochloric acid and 1.0 to 20 vol% hydrogen peroxide water, or 1.0 to 10 vol. 2. The method for analyzing metal impurities in silicon powder according to claim 1, which is a mixed solution of 1% hydrofluoric acid and 1.0 to 20 vol% hydrogen peroxide solution.
請求項２に記載の発明によれば、上記第１の混合溶液は、１．０〜３７ｖｏｌ％の塩酸または１．０〜１０ｖｏｌ％のフッ酸と、１．０〜２０ｖｏｌ％の過酸化水素水との混合溶液である。この濃度の範囲において、シリコン粉の表面に付着している金属不純物を溶解することができる。
第１の混合溶液中の塩酸の濃度が１．０ｖｏｌ％未満の場合、金属不純物を溶解することができない。第１の混合溶液中の塩酸の濃度の上限は３７ｖｏｌ％、つまり塩化水素の飽和水溶液である。
第１の混合溶液中の過酸化水素の濃度が１．０ｖｏｌ％未満の場合、金属不純物の溶解度をあげることができない。過酸化水素は、金属を塩酸で溶解させる際に触媒として作用する。第１の混合溶液中の過酸化水素の濃度が２０ｖｏｌ％を超える場合、シリコン粉に酸化膜が形成され、金属不純物を溶解することができない。
第１の混合溶液中のフッ酸の濃度が１．０ｖｏｌ％未満の場合、金属不純物を溶解することができない。第１の混合溶液中のフッ酸の濃度が１０ｖｏｌ％を超える場合、シリコン粉自体が溶解され、シリコン粉の表面に付着した金属不純物のみを分析することができない。
第１の混合溶液中の塩酸と過酸化水素水、またはフッ酸と過酸化水素水との体積割合は任意であるが、１：１が好ましい。塩酸と過酸化水素水またはフッ酸と過酸化水素水の体積割合が１：１である場合、この第１の混合溶液による化学反応の量論関係に無駄がない。
According to invention of Claim 2, the said 1st mixed solution is 1.0-37 vol% hydrochloric acid or 1.0-10 vol% hydrofluoric acid, and 1.0-20 vol% hydrogen peroxide water. And a mixed solution. In this concentration range, metal impurities adhering to the surface of the silicon powder can be dissolved.
When the concentration of hydrochloric acid in the first mixed solution is less than 1.0 vol%, the metal impurities cannot be dissolved. The upper limit of the concentration of hydrochloric acid in the first mixed solution is 37 vol%, that is, a saturated aqueous solution of hydrogen chloride.
When the concentration of hydrogen peroxide in the first mixed solution is less than 1.0 vol%, the solubility of metal impurities cannot be increased. Hydrogen peroxide acts as a catalyst when dissolving metals with hydrochloric acid. When the concentration of hydrogen peroxide in the first mixed solution exceeds 20 vol%, an oxide film is formed on the silicon powder and the metal impurities cannot be dissolved.
When the concentration of hydrofluoric acid in the first mixed solution is less than 1.0 vol%, the metal impurities cannot be dissolved. When the concentration of hydrofluoric acid in the first mixed solution exceeds 10 vol%, the silicon powder itself is dissolved, and it is not possible to analyze only the metal impurities attached to the surface of the silicon powder.
The volume ratio of hydrochloric acid and hydrogen peroxide solution or hydrofluoric acid and hydrogen peroxide solution in the first mixed solution is arbitrary, but 1: 1 is preferable. When the volume ratio of hydrochloric acid and hydrogen peroxide solution or hydrofluoric acid and hydrogen peroxide solution is 1: 1, there is no waste in the stoichiometric relationship of the chemical reaction by the first mixed solution.
請求項３に記載の発明は、上記静置する時間は５時間以上である請求項１または請求項２に記載のシリコン粉の金属不純物の分析方法である。 Invention of Claim 3 is the analysis method of the metal impurity of the silicon | silicone powder of Claim 1 or Claim 2 whose said standing time is 5 hours or more.
請求項３に記載の発明によれば、上記第１の混合溶液を上記シリコン粉に加えた後、５時間以上静置する。５時間以上静置することにより、シリコン粉の表面に付着した金属不純物を溶解するとともに、第１の混合溶液とシリコン粉とを完全に固液分離することができる。
静置時間が５時間未満の場合、上記第１の混合溶液とシリコン粉とを完全に固液分離することができない。
According to invention of Claim 3, after adding the said 1st mixed solution to the said silicon powder, it leaves still for 5 hours or more. By allowing to stand for 5 hours or longer, the metal impurities attached to the surface of the silicon powder can be dissolved, and the first mixed solution and the silicon powder can be completely solid-liquid separated.
When the standing time is less than 5 hours, the first mixed solution and the silicon powder cannot be completely solid-liquid separated.
請求項４に記載の発明は、上記第２の混合溶液中の塩酸の濃度は５〜２０ｖｏｌ％であり、この第２の混合溶液中の硝酸の濃度は５〜４０ｖｏｌ％であり、この第２の混合溶液中のフッ酸の濃度は５〜３０ｖｏｌ％である請求項１〜請求項３のいずれか１項に記載のシリコン粉の金属不純物の分析方法である。 In the invention according to claim 4, the concentration of hydrochloric acid in the second mixed solution is 5 to 20 vol%, and the concentration of nitric acid in the second mixed solution is 5 to 40 vol%. The method for analyzing metal impurities in silicon powder according to any one of claims 1 to 3, wherein the concentration of hydrofluoric acid in the mixed solution is 5 to 30 vol%.
請求項４に記載の発明によれば、上記第２の混合溶液中の塩酸の濃度は５〜２０ｖｏｌ％である。この第２の混合溶液中の硝酸の濃度は５〜４０ｖｏｌ％である。また、この第２の混合溶液中のフッ酸の濃度は５〜３０ｖｏｌ％である。この濃度の範囲において、シリコン粉の内部のすべての金属不純物を溶解することができる。つまり、シリコン粉の内部の水素よりイオン化傾向の低い金属を含めたすべての金属不純物を溶解することができる。
水素よりイオン化傾向の低い物質を溶かすことができるのは、第２の混合溶液に塩酸と硝酸とが含まれているためである。この塩酸と硝酸との混合溶液は通称、王水とよばれる。この王水の作用によって金属不純物を溶解することができる。フッ酸が含まれるのは、シリコン粉を効率よく溶解するためである。
第２の混合溶液中の塩酸の濃度が５ｖｏｌ％未満の場合、または、硝酸の濃度が５ｖｏｌ％の場合、金属不純物を溶解することができない。また、第２の混合溶液中の塩酸の濃度が２０ｖｏｌ％を超える場合、または、硝酸の濃度が４０ｖｏｌ％を超える場合、混合溶液の酸性度が強すぎるため、取り扱いが困難である。
第２の混合溶液中のフッ化水素の濃度が５ｖｏｌ％未満の場合、シリコン粉を完全に溶解することができない。フッ酸の濃度が３０ｖｏｌ％を超える場合、取り扱いが困難である。
According to invention of Claim 4, the density | concentration of hydrochloric acid in the said 2nd mixed solution is 5-20 vol%. The concentration of nitric acid in the second mixed solution is 5 to 40 vol%. Moreover, the density | concentration of the hydrofluoric acid in this 2nd mixed solution is 5-30 vol%. In this concentration range, all metal impurities inside the silicon powder can be dissolved. That is, it is possible to dissolve all metal impurities including a metal having a lower ionization tendency than hydrogen in the silicon powder.
The reason why the substance having a lower ionization tendency than hydrogen can be dissolved is because the second mixed solution contains hydrochloric acid and nitric acid. This mixed solution of hydrochloric acid and nitric acid is commonly called aqua regia. Metal impurities can be dissolved by the action of this aqua regia. The reason why hydrofluoric acid is contained is to dissolve silicon powder efficiently.
When the concentration of hydrochloric acid in the second mixed solution is less than 5 vol%, or when the concentration of nitric acid is 5 vol%, the metal impurities cannot be dissolved. Moreover, when the density | concentration of hydrochloric acid in a 2nd mixed solution exceeds 20 vol%, or the density | concentration of nitric acid exceeds 40 vol%, since the acidity of a mixed solution is too strong, handling is difficult.
When the concentration of hydrogen fluoride in the second mixed solution is less than 5 vol%, the silicon powder cannot be completely dissolved. When the concentration of hydrofluoric acid exceeds 30 vol%, handling is difficult.
請求項５に記載の発明は、上記加熱溶解工程での加熱温度は５０〜３００℃である請求項１〜請求項４のいずれか１項に記載のシリコン粉の金属不純物の分析方法である。 Invention of Claim 5 is the analysis method of the metal impurity of the silicon | silicone powder of any one of Claims 1-4 whose heating temperature in the said heating melt | dissolution process is 50-300 degreeC.
上記加熱溶解工程での加熱温度が５０〜３００℃に設定することで、金属不純物の溶解時間を短縮することができる。
上記加熱温度が５０℃未満の場合、金属不純物の溶解に時間がかかる。加熱温度が３００℃を超える場合、第２の容器が変形する。
By setting the heating temperature in the heating and melting step to 50 to 300 ° C., the melting time of the metal impurities can be shortened.
When the heating temperature is less than 50 ° C., it takes time to dissolve the metal impurities. When the heating temperature exceeds 300 ° C., the second container is deformed.
本発明によれば、第１の混合溶液と第２の混合溶液とを用いることで、イオン化傾向の高低に拘わらず、金属不純物をこれらの混合溶液に溶解させることができる。このため、ＩＣＰ発光分析などの分析機器により精度の高い分析が可能となる。また、第１の混合溶液と第２の混合溶液とを用いることで、シリコン粉の表面の金属不純物とシリコン粉の内部の金属不純物とを区別して分析することができる。 According to the present invention, by using the first mixed solution and the second mixed solution, metal impurities can be dissolved in these mixed solutions regardless of the level of ionization. For this reason, analysis with high accuracy is possible by an analytical instrument such as ICP emission analysis. Further, by using the first mixed solution and the second mixed solution, the metal impurities on the surface of the silicon powder and the metal impurities inside the silicon powder can be distinguished and analyzed.
シリコンインゴットを機械加工してウェーハを製造する工程や、デバイス形成後のウェーハのバックグラインド工程などで多量に発生するシリコン粉（シリコンスラッジ）をＰＴＦＥ製の容器（第１の容器）に投入した。シリコン粉の投入量は１００ｇである。このシリコン粉には鉄、アルミニウム、銅、チタン、金、白金等の金属不純物が含まれている。なお、このシリコン粉はあらかじめ揮発性の高い有機溶剤（アセトンなど）により油分を除去している。このシリコン粉の粒径を粒度分布計（株式会社島津製作所製レーザ回折式粒度分布測定装置ＳＡＬＤ−３１００）を用いて測定した結果、１７μｍであった。また、粒径の大きいシリコン粉は、撹拌擂潰機にて最大粒径３０μｍ程度に粉砕した。 Silicon powder (silicon sludge) generated in a large amount in a process of machining a silicon ingot to manufacture a wafer, a back grinding process of a wafer after device formation, and the like was put into a PTFE container (first container). The input amount of silicon powder is 100 g. This silicon powder contains metal impurities such as iron, aluminum, copper, titanium, gold, and platinum. In addition, this silicon powder has previously removed oil with a highly volatile organic solvent (such as acetone). The particle size of this silicon powder was measured using a particle size distribution meter (Laser diffraction particle size distribution measuring device SALD-3100 manufactured by Shimadzu Corporation), and was found to be 17 μm. Further, the silicon powder having a large particle size was pulverized to a maximum particle size of about 30 μm by a stirring crusher.
上記第１の容器内のシリコン粉に、第１の混合溶液を５００ｍｌ加えた。この第１の混合溶液は、５ｖｏｌ％塩酸と、５ｖｏｌ％過酸化水素水との混合溶液である。この第１の混合溶液は、具体的には、市販の塩酸と市販の過酸化水素水とを配合して製造される。この第１の混合溶液には異物は含まれていない。
その後、１０時間静置した。静置とは、容器に振動を与えずに、または容器内の内容物を撹拌せずに、溶液とシリコン粉とを固液分離することである。
静置後の、第１の混合溶液は、透明であった。この透明な第１の混合溶液を５ｍｌ採取し、ＩＣＰ−ＭＳにて分析したところ、鉄、アルミニウムが検出された。つまり、シリコン粉の表面に付着していた金属不純物が第１の混合溶液に溶解していることが判明した。静置している間、シリコン粉に付着していた鉄、アルミニウムは（１）〜（２）の反応が起きていることが判明した。
Ｆｅ＋２ＨＣｌ→Ｆｅ２＋＋２Ｃｌ−＋Ｈ２（水溶液中での反応）・・・（１）
Ａｌ＋２ＨＣｌ→Ａｌ３＋＋２Ｃｌ−＋Ｈ２（水溶液中での反応）・・・（２）
ＩＣＰ−ＭＳは、サーモフィッシャーサイエンティフィック株式会社製ＥＬＥＭＥＮＴ２を用いた。このＩＣＰ−ＭＳでは、２７．１２ＭＨｚプラズマにより試料を確実にイオン化することが可能となる。
500 ml of the first mixed solution was added to the silicon powder in the first container. This first mixed solution is a mixed solution of 5 vol% hydrochloric acid and 5 vol% hydrogen peroxide. Specifically, the first mixed solution is produced by blending commercially available hydrochloric acid and a commercially available hydrogen peroxide solution. This first mixed solution contains no foreign matter.
Then, it left still for 10 hours. The standing is to solid-liquid separate the solution and the silicon powder without applying vibration to the container or stirring the contents in the container.
The first mixed solution after standing was transparent. When 5 ml of this transparent first mixed solution was collected and analyzed by ICP-MS, iron and aluminum were detected. That is, it was found that the metal impurities adhering to the surface of the silicon powder were dissolved in the first mixed solution. It was found that the reactions (1) to (2) occurred in the iron and aluminum adhered to the silicon powder during the standing.
Fe + 2HCl → Fe 2+ + 2Cl − + H 2 (reaction in aqueous solution) (1)
Al + 2HCl → Al 3+ + 2Cl − + H 2 (reaction in aqueous solution) (2)
ICP-MS used ELEMENT2 manufactured by Thermo Fisher Scientific Co., Ltd. In this ICP-MS, the sample can be reliably ionized by the 27.12 MHz plasma.
静置後のシリコン粉をろ過により第１の容器から取り出し、耐熱性を有するＰＴＦＥ製の容器（第２の容器）に投入した。
その後、このシリコン粉に第２の混合溶液を加えた。この第２の混合溶液は、９ｖｏｌ％塩酸と、１５ｖｏｌ％硝酸と、１３ｖｏｌ％フッ酸との混合水溶液である。具体的には、この第２の混合溶液は、市販の塩酸と、市販の硝酸と、市販のフッ酸とを配合して製造される。この第２の混合溶液には異物が含まれていない。この第２の混合溶液を９０ｇ加えた。その後、ホットプレートにてこのシリコン粉を含む第２の混合溶液を２００℃まで加熱し、この第２の混合溶液を蒸発させた。蒸発後の残留物は白色であっため、蒸発の際に析出した金属不純物であることが判明した。蒸発している間、シリコン粉は（３）と（４）の反応が起きていることが判明した。
Ｓｉ＋４ＨＮＯ３→ＳｉＯ２＋４ＮＯ２↑＋２Ｈ２Ｏ ・・・（３）
ＳｉＯ２＋４ＨＦ→ＳｉＦ４↑＋２Ｈ２Ｏ ・・・（４）
四フッ化ケイ素はガスの状態となって大気に放出される。この四フッ化ケイ素は有毒物質であるため、ドラフトチャンバ内で本作業を行った。また、硝酸にてシリコン粉を酸化させ、フッ酸にてシリコン酸化物から四フッ化ケイ素を発生させ、第２の容器の外に放出することにより、完全にシリコン粉を除去することができる。
なお、第２の容器をＰＴＦＥ製にするのは、高温に耐えられて不純物の溶出が少ない容器であるためである。
The silicon powder after standing was taken out from the first container by filtration and put into a PTFE container (second container) having heat resistance.
Thereafter, the second mixed solution was added to the silicon powder. This second mixed solution is a mixed aqueous solution of 9 vol% hydrochloric acid, 15 vol% nitric acid, and 13 vol% hydrofluoric acid. Specifically, the second mixed solution is manufactured by blending commercially available hydrochloric acid, commercially available nitric acid, and commercially available hydrofluoric acid. The second mixed solution does not contain foreign matters. 90 g of this second mixed solution was added. Then, the 2nd mixed solution containing this silicon powder was heated to 200 degreeC with the hotplate, and this 2nd mixed solution was evaporated. Since the residue after evaporation was white, it was found to be a metal impurity deposited during evaporation. During the evaporation, the silicon powder was found to undergo the reactions (3) and (4).
Si + 4HNO 3 → SiO 2 + 4NO 2 ↑ + 2H 2 O (3)
SiO 2 + 4HF → SiF 4 ↑ + 2H 2 O (4)
Silicon tetrafluoride is released into the atmosphere as a gas. Since this silicon tetrafluoride is a toxic substance, this work was performed in a draft chamber. Further, the silicon powder can be completely removed by oxidizing the silicon powder with nitric acid, generating silicon tetrafluoride from the silicon oxide with hydrofluoric acid, and releasing it from the second container.
Note that the second container is made of PTFE because it is a container that can withstand high temperatures and has little impurity elution.
その後、析出した金属不純物に再度第２の混合溶液を１０ｇ加えた。そして、ドラフトチャンバ内でホットプレートにてこの第２の混合溶液を２００℃まで加熱した。この加熱した第２の混合溶液を５ｍｌ採取し、ＩＣＰ−ＭＳにて分析した。この結果、金、白金が検出された。つまり、シリコン内部に存在するイオン化傾向が水素より低い金属の不純物が第２の混合溶液に溶解していることが判明した。加熱中において、金や白金は王水の作用により溶解していることが判明した（（５）〜（７）の反応が起きている）。
ＨＮＯ３＋３ＨＣｌ→ＮＯＣｌ＋Ｃｌ２＋２Ｈ２Ｏ ・・・（５）
Ａｕ＋ＮＯＣｌ＋Ｃｌ２＋ＨＣｌ→ＨＡｕＣｌ４＋ＮＯ ・・・（６）
Ｐｔ＋２ＮＯＣｌ＋Ｃｌ２＋２ＨＣｌ→Ｈ２ＰｔＣｌ６＋２ＮＯ ・・・（７）
Thereafter, 10 g of the second mixed solution was added again to the precipitated metal impurities. And this 2nd mixed solution was heated to 200 degreeC with the hotplate in the draft chamber. 5 ml of this heated second mixed solution was collected and analyzed by ICP-MS. As a result, gold and platinum were detected. In other words, it has been found that metal impurities present in silicon and having a lower ionization tendency than hydrogen are dissolved in the second mixed solution. During the heating, it was found that gold and platinum were dissolved by the action of aqua regia (the reactions (5) to (7) occurred).
HNO 3 + 3HCl → NOCl + Cl 2 + 2H 2 O (5)
Au + NOCl + Cl 2 + HCl → HAuCl 4 + NO (6)
Pt + 2NOCl + Cl 2 + 2HCl → H 2 PtCl 6 + 2NO (7)
次に、本発明のシリコン粉の金属不純物の分析方法の分析精度を確認するために実験を行った。 Next, an experiment was conducted to confirm the analysis accuracy of the method for analyzing metal impurities of silicon powder of the present invention.
金属不純物が含まれていないシリコン粉１００ｇ（平均粒径１７μｍ）に、鉄０．１ｍｇ（和光純薬工業株式会社製、鉄Powder）、アルミニウム０．１ｍｇ（和光純薬工業株式会社製、アルミニウムPowder）、金０．０５ｍｇ（和光純薬工業株式会社製、金粉）、白金０．０５ｍｇ（和光純薬工業株式会社製、白金粉）を加え、撹拌を行い、サンプル粉を得た。
このサンプル粉に対し、上述の金属不純物の分析方法の手順と同じ手順にて処理を行った。そして、静置後の第１の混合溶液と、加熱後の第２の混合溶液をそれぞれ５ｍｌ採取し、ＩＣＰ−ＭＳにて分析を行った。
ＩＣＰ−ＭＳでの分析結果を表１に示す。
100 g of silicon powder (average particle size 17 μm) containing no metal impurities, 0.1 mg of iron (Wako Pure Chemical Industries, Ltd., Iron Powder), 0.1 mg of aluminum (Wako Pure Chemical Industries, Ltd., Aluminum Powder) ), 0.05 mg of gold (made by Wako Pure Chemical Industries, Ltd., gold powder) and 0.05 mg of platinum (made by Wako Pure Chemical Industries, Ltd., platinum powder) were added and stirred to obtain a sample powder.
This sample powder was processed in the same procedure as that of the above-described method for analyzing metal impurities. Then, 5 ml of each of the first mixed solution after standing and the second mixed solution after heating was collected and analyzed by ICP-MS.
The analysis results by ICP-MS are shown in Table 1.
この結果から、静置後の第１の混合溶液にはシリコン粉の表面に多く存在する鉄やアルミニウムが９８〜９９％検出されたことが判明した。
また、加熱後の第２の混合溶液には、シリコン粉の内部に多く存在する低い金や白金が９６〜９８％検出されたことが判明した。
このことから、本発明の分析方法は、シリコン粉の表面に付着している金属不純物と、シリコン粉の内部に存在する金属不純物とを区別して精度良く分析することができることが判明した。
また、本発明に係る分析を終えた後、ＩＣＰ−ＭＳのネブライザーの目詰まりは確認できなかった。
From this result, it was found that 98 to 99% of iron or aluminum present in the surface of the silicon powder was detected in the first mixed solution after standing.
Moreover, it turned out that 96-98% of low gold | metal | money and platinum which exist a lot in the inside of silicon powder were detected in the 2nd mixed solution after a heating.
From this, it was found that the analysis method of the present invention can accurately analyze the metal impurities adhering to the surface of the silicon powder and the metal impurities existing inside the silicon powder.
Moreover, after finishing the analysis according to the present invention, clogging of the nebulizer of ICP-MS could not be confirmed.
本実験から、本発明に係るシリコン粉の金属不純物の分析方法によれば、シリコン粉に含まれる金属不純物を第１の混合溶液又は第２の混合溶液に溶解することができることが判明した。また、ＩＣＰ−ＭＳにより金属不純物をイオン化させ、精度良く分析ができることが判明した。さらに、目詰まりが発生せず、ＩＣＰ−ＭＳを故障させることなく分析を行うことができることが判明した。 From this experiment, it was found that the metal impurity contained in the silicon powder can be dissolved in the first mixed solution or the second mixed solution according to the method for analyzing metal impurities in the silicon powder according to the present invention. Further, it was found that the metal impurities can be ionized by ICP-MS and the analysis can be performed with high accuracy. Furthermore, it has been found that clogging does not occur and analysis can be performed without damaging the ICP-MS.
Claims (5)
その後、上記シリコン粉を第１の容器から取り出し、第２の容器に入れ、塩酸と、硝酸と、フッ酸とからなる第２の混合溶液をこのシリコン粉に加え、四フッ化ケイ素を発生させ、この四フッ化ケイ素を第２の容器の外に放出するシリコン反応工程と、
その後、この第２の混合溶液を蒸発させることにより金属不純物を析出させる蒸発工程と、
上記蒸発工程後、析出した金属不純物に新たに第２の混合溶液を加え、これを加熱し、析出した金属不純物を溶解させる加熱溶解工程と、
上記加熱溶解工程後、析出した金属不純物を溶解した第２の混合溶液を採取し、この第２の混合溶液に溶解した金属不純物の濃度を測定する金属分析工程と、を有するシリコン粉の金属不純物の分析方法。 Silicon powder containing metal impurities is put into a first container, and a first mixed solution composed of hydrochloric acid and hydrogen peroxide solution or hydrofluoric acid and hydrogen peroxide solution is added to the silicon powder and left for a predetermined time. A metal impurity dissolving step for dissolving the metal impurities adhering to the surface of the silicon powder,
Thereafter, the silicon powder is taken out from the first container, placed in the second container, and a second mixed solution composed of hydrochloric acid, nitric acid and hydrofluoric acid is added to the silicon powder to generate silicon tetrafluoride. A silicon reaction step of releasing the silicon tetrafluoride out of the second container;
Thereafter, an evaporation step of depositing metal impurities by evaporating the second mixed solution;
After the evaporation step, a second mixed solution is newly added to the precipitated metal impurities, this is heated, and a heating and dissolving step for dissolving the precipitated metal impurities,
After the heating and dissolving step, a second mixed solution in which the deposited metal impurities are dissolved is collected, and a metal analyzing step for measuring the concentration of the metal impurities dissolved in the second mixed solution is included. Analysis method.
この第２の混合溶液中の硝酸の濃度は５〜４０ｖｏｌ％であり、
この第２の混合溶液中のフッ酸の濃度は５〜３０ｖｏｌ％である請求項１〜請求項３のいずれか１項に記載のシリコン粉の金属不純物の分析方法。 The concentration of hydrochloric acid in the second mixed solution is 5 to 20 vol%,
The concentration of nitric acid in the second mixed solution is 5 to 40 vol%,
The method for analyzing metal impurities in silicon powder according to any one of claims 1 to 3, wherein the concentration of hydrofluoric acid in the second mixed solution is 5 to 30 vol%.
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